CN101959598A - Regeneration of hydrogenation catalysts based on a platinum metal - Google Patents

Regeneration of hydrogenation catalysts based on a platinum metal Download PDF

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CN101959598A
CN101959598A CN2009801073420A CN200980107342A CN101959598A CN 101959598 A CN101959598 A CN 101959598A CN 2009801073420 A CN2009801073420 A CN 2009801073420A CN 200980107342 A CN200980107342 A CN 200980107342A CN 101959598 A CN101959598 A CN 101959598A
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catalyst
platinum
regeneration
acid
hydrogenation
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CN2009801073420A
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CN101959598B (en
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G·拉迪乌斯
B·范德斯特拉腾
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巴斯夫欧洲公司
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Priority to PCT/EP2009/052427 priority patent/WO2009112386A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/14—Hydroxylamine; Salts thereof
    • C01B21/1409—Preparation
    • C01B21/1418—Preparation by catalytic reduction of nitrogen oxides or nitrates with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

Disclosed is a method for regenerating hydrogenation catalysts based on a platinum metal, in which the hydrogenation catalysts based on a platinum metal are thermally regenerated at temperatures ranging from 50 to 600 DEG C.

Description

Regeneration based on the hydrogenation catalyst of platinum

The present invention relates to based on the regeneration of the hydrogenation catalyst of platinum and---minimizing of the amount of undesirable catalyst poison if desired---, and relate to their purposes as hydrogenation catalyst is particularly in the preparation hydroxyl ammonium salt.

For will be for the reaction of carrying out in the presence of catalyst of industrial enforcement, the preparation of catalyst system therefor and the expense of regeneration, activity, selectivity and life-span be very important.This point thereby also be applicable in acid solution by hydrogen catalysis reduction nitric oxide and form hydroxyl ammonium salt.In the method, use the hydrogenation catalyst that contains platinum usually.

EP-A-620 042 discloses a kind of method that makes platinum catalyst regeneration, wherein, regenerate by following steps with the platinum metal catalyst of crossing: the platinum in this catalyst is dissolved in the solution by a kind of acid or a kind of acid blend,, isolates indissolvable component if suitable; Neutralize resulting platinum salting liquid and it is imposed on a kind of carrier, and if suitable, it is mixed with finely divided sulphur; The platinum salt that obtains by the reduction of a kind of reducing agent subsequently, if desired, before with finely divided sulphuring treatment, in the process or add a kind of carrier material afterwards.Hydrogenation catalyst based on platinum is polluted in the use that also preferably occurs in usually under the reaction condition by undesirable catalyst poison, but also can occur in its preparation or the regenerative process.Undesirable catalyst poison usually with raw material, particularly with sulfuric acid, be introduced in the catalyst or cause on the catalyst.Especially, these catalyst poisons can't be isolated from activity of such catalysts platinum or only can be separated to not satisfied degree by the renovation process among the EP-A-620 042.

Therefore, a target of the present invention is to revise above-mentioned shortcoming.Another target of the present invention can be and makes hydrogenation catalyst regeneration, this hydrogenation catalyst was compared with the performance that preparation reaches during this hydrogenation catalyst before regeneration next time, have activity special setting, higher, lower or suitable and/or selectivity, and/or shorter, preferred suitable or longer service life.

Correspondingly, we have found a kind of new, improved method that makes based on the hydrogenation catalyst regeneration of platinum, in the method, regenerate 50-600 ℃ temperature based on the hydrogenation catalyst of platinum.

Making can be by following enforcement based on the inventive method of the hydrogenation catalyst of platinum heat regeneration:

Hydrogenation catalyst based on platinum can not carry out under the situation of prepurification, or preferably after prepurification, be generally 50-600 ℃, preferred 100-450 ℃, especially preferred 120-400 ℃ temperature and preferably regenerate in an inert atmosphere.The duration of heat regeneration should be no less than 0.5h usually, is generally 0.5-10000h, preferred 1-100h, preferred especially 5-80h, particularly 12-60h.

Suitable inert gas is for being all gas of inertia under hot regeneration condition, nitrogen for example, or rare gas such as helium or argon gas, or the mixture of these gases, or mainly contain, promptly contain at least 60 volume %, preferred at least 75 volume %, preferred especially at least 85 volume %, the particularly admixture of gas of at least 95 volume % inert gases.In a preferred embodiment, in the gas phase ratio of oxygen usually should less than 1 volume %, preferably less than 0.1 volume %, especially preferably less than 100 volume ppm.Pressure in the gas phase itself is inessential.Preferred absolute pressure is usually in the 0.01-100bar scope, preferably in the 0.1-10bar scope, between the limit value particularly preferably in following 100mbar of atmospheric pressure and the above 100mbar of atmospheric pressure.

Be the described hydrogenation catalyst of prepurification, can treat the discontinuous washing of hydrogenation catalyst of regeneration or continuous washing until being neutral, so that the pH of cleaning solution is in the scope of 5-8, preferred 5.5-7.5, preferred especially 6-7.For this reason, advantageously, whole cleaning solutions of amount is divided into several parts and wash (flushing) in this mode in a plurality of substeps.

Suitable cleaning solution has river, if suitable filtered river, running water, deionized water, particularly deionized water.If suitable, also cleaning solution partly or wholly can be circulated, preferably partly circulate.Particularly preferably in using deionized water under the situation about not circulating.

Before heat regeneration, before or after using the cleaning solution prepurification, preferably after heat regeneration, available a kind of strong acid treatment hydrogenation catalyst, handling in the various situations can be moistening, under part drying or drying or dried state, at 0-150 ℃, preferred 10-120 ℃, preferred especially 75-105 ℃ temperature or in room temperature (environment temperature) (18-28 ℃) with at 0.1-100bar, preferred 0.5-50bar, under the absolute pressure of preferred especially 0.9-5bar, particularly under atmospheric pressure carry out, and after with strong acid treatment, preferably use cleaning solution to carry out the back purifying with the similar mode of prepurification with a kind of.

Suitable strong acid has strong inorganic acid, for example (concentration is 30-95 weight %, preferred 50-80 weight %, preferred especially 60-70 weight % to nitric acid, red fuming nitric acid (RFNA) particularly), (concentration is 15-98 weight %, preferred 20-97 weight %, preferred especially 90-97 weight % to sulfuric acid, the concentrated sulfuric acid particularly), (concentration is 15-50 weight %, preferred 20-45 weight %, preferred especially 30-40 weight % to hydrochloric acid, or its mixture concentrated hydrochloric acid particularly); Strong monocarboxylic acid, for example formic acid, acetate or propionic acid, or its mixture, or dicarboxylic acids, for example oxalic acid; Or two kinds to five kinds, preferred two or three, preferred especially two kinds are selected from inorganic acid, the mixture of identical or different class strong acid in monocarboxylic acid and the dicarboxylic acids, (concentration is 30-95 weight % to preferred nitric acid, preferred 50-80 weight %, preferred especially 60-70 weight %, red fuming nitric acid (RFNA) particularly), (concentration is 15-98 weight % to sulfuric acid, preferred 20-97 weight %, preferred especially 90-97 weight %, the concentrated sulfuric acid particularly), (concentration is 15-50 weight % to hydrochloric acid, preferred 20-45 weight %, preferred especially 30-40 weight %, concentrated hydrochloric acid particularly), or its mixture, special preferred molar ratio is 0.25: 1 to 4: 1 the hydrochloric acid and the mixture of nitric acid, chloroazotic acid (mol ratio of hydrochloric acid and nitric acid is 3: 1) particularly is particularly by mixing the chloroazotic acid that dense strong acid obtains.

Below to the description of regeneration for example can be applicable on a small scale laboratory scale, to the discontinuous or continuous process of commercial scale or large scale industry scale; in the preferred continuous process, by realizing by the alternative hydrogenation catalyst that is used to regenerate that takes out of the hydrogenation catalyst of new preparation or regeneration.The suitable device that is used to regenerate or the capacity of container depend on the scale of implementing hydrogenation process, also depend on the amount of catalyst to be regenerated.In industrial process or large scale industry process, regeneration can be carried out continuously or discontinuously.

The regeneration of the heat of hydrogenation catalyst can be designed to catalyst is stored in suitable device or the container to be carried out.This embodiment is suitable especially to the situation of industrial process or large scale industry process.

Exemplary (above-mentioned boundary condition, for example temperature, pressure, raw material and ratio are applicable to this similarly, even only exemplarily indicate hereinafter):

Hydrogenation catalyst can shift out from course of reaction in batches or take out before regeneration.If suitable, many parts of catalyst that take out are handled successively.

As indicated above, the catalyst that from course of reaction, takes out can suitable filter for example flat filter (flat filter) (as filter-press or plain net filter (fiat-bed filter)) or for example have on the filter of filter core (filter candle insert) wash until being neutral with cleaning solution.Washing can be carried out continuously or discontinuously.

Subsequently, if can be with catalyst---suitable, after other treatment steps, after for example regenerating with strong acid---transfer in the device that is suitable for regeneration, preferably regenerate without strong acid according to the present invention.

Particularly preferred airtight, the preferred especially bubble-tight case of suitable device or container can be introduced catalyst in this case, and can be provided with gas and discharge gas by at least one outlet again by at least one inlet tube.In the present invention, air-tightness means, and for example when inlet and the valve of outlet line are closed at least 30 minutes, the gauge pressure of 0.5bar reduces and is no more than 100mbar, preferably 30mbar only.

The gas of introducing heats or heats in this closed box before can be in entering this closed box, thereby makes gas phase reach preferred regeneration temperature.For obtaining better to regenerate the result, catalyst preferably is separated into thin layer in case, thus but utmost point heatable catalyst composition equably.The thickness of described layer can be less than 50cm, preferably less than 15cm, particularly less than 1cm.

Should select air-flow, make few catalyst granules, preferably do not have a catalyst granules generation fluidisation; In the present invention, fluidisation is meant catalyst granules generation turn (swirl up).The limit value to gas velocity like this depends on the size distribution of catalyst solid and can carry out arithmetic and estimate or measuring.Preferably gas velocity is selected, is made through after the period of storage, the reduction of drying solid quality be not more than 10 weight %, preferably be not more than 5 weight %, particularly be not more than 1 weight %.Air-flow can produce by suitable air blast, for example compressor such as hot air blowers or liquid piston compressor; Or the pressure by reducing gases at high pressure is to required pressure, and for example reducing gauge pressure is that nitrogen gas pressure (for example in orifice plate) to the required pressure that exists in the loop systems of 10bar produces.Also gas velocity for example can be transferred to maximum output by the design to orifice plate then, and can for example regulate by hand-operated valve or electronic control valve.

Suitable device also can have an exhaust treatment system.This system comprises for example gas cooler, this cooler the hot gas of discharging can be cooled to less than 200 ℃, preferably less than 100 ℃ temperature.About gas cooler, can use conventional heat exchanger, for example aerial cooler, shell-and-tube exchanger or heat-exchangers of the plate type.The downstream of described gas cooler can be a precipitation vessel, the precipitable any condensing gas component of this container or its solid particle that carries.Can use for example simple gas deflection container (gas deflection vessel) or cyclone separator herein.The setting of gas-cooled setting and precipitation is not a key of the present invention.

After period of storage finishes, catalyst is cooled to environment temperature in protective atmosphere.Particularly keeping described protective atmosphere reduces to below 40 ℃ until solid temperature.For quickening this cooling procedure, can in regenerating unit, blast cold protective gas; Equally, gas velocity must remain on below the fluidisation limit value.For protective gas, the preferred inert gas that also in heating process, uses that uses.

If suitable, catalyst can be carried out other processing before introducing in the production process again, for example described in present patent application, regenerate by strong acid.Implementing other treatment steps is not the sin qua non, but preferably handles with strong acid before introducing catalyst in the production process again.

Hot regeneration of the present invention can be played increases activity of such catalysts and/or optionally effect.Also can increase the service life of catalyst between twice regeneration in this mode.Catalyst activity or optionally formerly reduce or the shortening in catalyst service life, particularly can cause by introduce catalyst poison in the catalyst and/or that cause on the catalyst with the raw material of production process, described raw material is hydrogen, nitric oxide particularly, and inorganic acid, as sulfuric acid or hydrochloric acid, particularly sulfuric acid; Or cause strong acid treatment process and causing for example by the catalyst treatment process.Described poisonous substance can be from the material of metal or slaine kind, and the metal in described metal or the described slaine particularly belongs to iron, manganese, chromium, nickel, copper, aluminium, mercury.Sulphur, arsenic and selenium and the compound that contains these elements also are known catalyst poisons.Catalyst poison is copper, mercury, sulphur, arsenic and selenium particularly, and the utmost point is copper, mercury and selenium particularly, and the utmost point is mercury and contain the compound of these elements especially.The mixing of the mixture of the compound of these elements or these elements itself also can be a catalyst poison.Generally speaking, described element has the effect of strong reduction activity sometimes, particularly during the concentration limit of each element that records in being higher than the dry catalyst composition.These concentration limits depend on each element and this catalyst situation of always poisoning, and promptly the concentration with the element of mentioning as catalyst poison becomes, and this concentration is based on the dry mass meter of catalyst.Particularly, the concentration of each element of mentioning as catalyst poison should be no more than 1000 ppm by weight, preferred 500 ppm by weight, particularly 300 ppm by weight usually.The concentration of mercury or the copper compound no matter of other elements of catalyst poison effect or these elements---how play separately---should be no more than 1000 ppm by weight, preferred 500 ppm by weight, particularly 300 ppm by weight usually.For avoiding surpassing these limit values or, can use renovation process of the present invention, particularly be used for reducing the concentration of mercury for revising the situation that surpasses this limit value.

Although when may having carried out repeatedly handling to catalyst,, can use hot renovation process of the present invention so that be the output of basic chemical process when still no longer enough high with above-mentioned hydrogenation catalyst based on platinum with strong acid.Determine catalyst is used whether necessary measuring of hot renovation process of the present invention, on measuring carbon monoxide-olefin polymeric the concentration of catalyst poison, particularly use the premeditated poisoning of the catalyst that sulphur carries out no longer can carry out or only can proceed to lower degree, and can not make activity of such catalysts increase to excessive degree, promptly preferably be no more than 5%.This sulfur poisoning situation is measured divided by the quality (in dry mass) of the catalyst of handling with this mode by being used in the sulfur content that adds in the renovation process that uses strong acid.Especially, when the dry mass meter based on catalyst to be regenerated, sulfur content is less than 1000 ppm by weight, particularly less than 200 ppm by weight, during especially less than 100 ppm by weight, use heat regeneration.

Therefore, hot renovation process of the present invention is a kind of activity of such catalysts level when the platinum metal that is fit to hydrogenation when being reduced to undesirable degree owing to the accumulation of catalyst poison on catalyst or catalyst carrier, increases the way of its activity level.The inventive method also can advantageously influence described selection of catalysts and/or service life.

Hydrogenation catalyst involved in the present invention can obtain by handling a kind of platinum salt and will being reduced to platinum with the platinum salt that this mode is handled subsequently usually.

Comprise the platinum of element form or be positioned at platinum on the carrier material based on the suitable hydrogenation catalyst of platinum, be preferably placed at the platinum on the carrier material.

Suitable carrier material has: silica (comprising quartz), aluminum oxide, for example Al 2O 3, AlO (OH), calcium oxide, titanium dioxide, the titanium dioxide of rutile, anatase form for example, active carbon or graphite; Preferred active carbon or graphite; Especially preferably only contain trace as his place of present patent application limit kind, the catalyst poison that may introduce by preliminary treatment or the graphite that does not contain this poisonous substance.

In principle, available platinum salt is all platinum salt that are suitable for regenerating, for example nickel salt, palladium salt, platinum salt, cobalt salt, rhodium salt, iridium salt and ruthenium salt, preferably palladium salt and platinum salt, especially preferably platinum salt.The water soluble salt of these metals, for example its halide, nitride and sulfate are suitable especially.Its example that can mention has:

-platinum (IV) compound, for example chloroplatinic acid and alkali metal salt thereof and ammonium salt, Tetrachloroplatinate salt or tetrachloro dihydroxy platinic acid;

-platinum (II) compound, for example Tetrachloroplatinate and alkali metal salt thereof, or platinum chloride (II);

-palladium (II) compound, for example acid of chlordene palladium and salt thereof, or palladium bichloride (II).

In principle, also can use the mixture that is mainly platinum or platinum salt and other slaines.

Undesirable catalyst poison is to be selected from the element of mercury, selenium, copper or the compound of these elements, is preferably selected from the element of mercury, copper or the compound of these elements, the compound of preferred especially mercury or this element.

Described undesirable catalyst poison usually with the raw material that is used for hydrogenation introduce catalyst or carrier, cause they the place and cause them.

When the catalyst poison on the carrier material was too fast owing to heat regeneration and/or chemical regeneration process reduce, catalyst may become too vivaciously and/or non-selectivity too.

In order to suppress described activity of such catalysts (if suitable) in set mode and to increase its selectivity (if suitable), can use catalyst poison to deliberate to poison in set mode.This process will be described as the part with strong acid treatment hereinafter.

The example of the suitable catalyst poison that can a kind of so set mode uses, promptly can set mode set activity of such catalysts, selectivity and/or service life and can have by washing and the process example of isolated catalyst poison from platinum that uses strong acid to regenerate by it, for example, sulphur or sodium dithionite (Na 2S 2O 4).

When sulphur was used for the part poisoning, the present invention used finely divided sulphur, for example coml " flowers of sulfur ".The preferred granularity of using is less than 500 μ m, preferably less than the sulphur of 50 μ m, special preferred size be distributed as wherein 20% particle less than 1 μ m, 50% particle less than 5 μ m and 90% particle sulphur (granularity is measured by for example MALVERN Mastersizer, referring to embodiment) less than 10 μ m.Suitable sulphur for example can be used as wettable sulphur " Kumulus WG " (BASF) is commercially available maybe and can obtains by known method itself, particularly sieved by the sulphur to for example flowers of sulfur or fine gtinding and obtain.

Generally speaking, with platinum salt in the aqueous solution with finely divided sulphuring treatment, undertaken by the finely divided sulphur of this aqueous metal salt and this is contacted.Described sulphur also can sulikol solution form use (referring to Jander-Blasius, Einf ü hrung in das anorganisch-chemische Praktikum, the 5th edition, 1964, the 415 pages).Described sulphur preferably adds with the form of water slurry.

In principle, preferred also available other solvents of aqueous solvent substitute and maybe they can be added in the water.Described sulphur also can dry powder form introduce in the solution of platinum salt.

In addition, dissolubility or the dispersed material that improves starting compound can be added in the reactant mixture.According to observation, the material that is specially adapted to this purpose is the dissolubility of improvement sulphur and all conventional surfactants of wetability.

Suitable surfactant---it is also referred to as dispersant---is at for example Ullmanns Der technischen Chemie, 4th edition, volume 23, Verlag Chemie, Weinheim, 1983, description is arranged among the pp.31-39.The example that can mention is:

Polyacrylate, polyvinylsulfonic acid ester class, PVP, TAMOL (BASF), Schaeffer salt and lignosulphonates.

In an especially preferred embodiment, the use lignosulphonates (be known in for example Ullmann, Der techn.Chemie, 4th edition, volume 16, p.253ff., and Verlag Chemie, 1978), the preferred alkali metal lignosulphonates that use, for example sodium lignosulfonate and lignin sulfonic acid potassium are as surfactant, and this is because when the washing catalyst finished product, they can easily be washed water and remove, and because their easily degradeds and can not polluting environment.

Described surfactant added in the reactant mixture add sulphur in platinum salt before usually, or advantageously, added in the water slurry of sulphur.

The weight ratio of surfactant and sulphur is chosen in the scope of 0.1-50 weight %, preferred 1-15 weight % usually.According to observation so far, can not produce deliquescent remarkable improvement greater than the surfactant of 50 weight %, and can not produce any clear improvement that can distinguish usually less than the amount of 0.1 weight % to sulphur.

With the temperature in the process of finely divided sulphuring treatment platinum salt usually 20-95 ℃, preferred 40-95 ℃, select in preferred 50-85 ℃ the scope especially.

Usually in the scope of 1.5-11.5, preferred 2.5-8.5, preferred especially 4.5-8.5, preferred extremely especially 5.6-6.2, select with the pH in the process of finely divided sulphuring treatment platinum salt.

Platinum salt passes through Na 2CO 3Being neutralized to pH is 3.0.Cushioning this solution with sodium acetate then, is 5.6-6.2 until reaching pH.

With the duration of finely divided sulphuring treatment platinum salt,, in 0.5-60min, preferred 2-15min scope, select usually promptly from adding finely divided sulphur to the time of adding reducing agent.Processing time is shorter than 0.5min and can causes catalyst poisoning insufficient usually, and according to former experience, the processing time is longer than 60min and there is no favourable part.

The mass ratio of sulphur and platinum is chosen in the scope of 0-30 weight %, preferred 0.5-15 weight % usually.

Carry out by advantageously adding a kind of reducing agent in the reactant mixture that after with finely divided sulphuring treatment platinum salt, obtains platinum salt being reduced to platinum after part poisons with sulphur.

Available reducing agent is all the common known reducing agents that are used for platinum salt is reduced to platinum, for example hydrazine, formaldehyde, formic acid or alkali metal formate or alkaline-earth metal formates, for example sodium formate, potassium formate and calcium formate, preferable formic acid especially.

The mol ratio of reducing agent and platinum is selected molar excess usually, preferred at least 2 times, preferred at least 10 times, preferred at least 40 times molar excess especially.

Temperature in the reduction process is chosen in 20-98 ℃, preferred 40-95 ℃, preferred especially 50-90 ℃ of scope usually.

After reaction is finished, catalyst carries out post processing usually in a usual manner, for example by it is leached from reactant mixture and advantageously water it is washed, preferably until the pH of the washings of discharging continuously or discontinuously in the scope of 5.0-7.0, preferred especially 6.0-7.0.

Therefore, the regeneration of using strong acid to carry out comprises

A) use the strong acid treatment catalyst,

B) if suitable, in and actified solution,

C) with catalyst poison for example sulphur set required degree of intoxication,

D) reduction platinum,

E) if suitable, the catalyst that washes regeneration with water is until being neutral.

Before use strong acid is regenerated, it is desirable to catalyzer with water is washed to neutral, but optional.Can before regenerating, implement use strong acid heat regeneration of the present invention then.

In a preferred embodiment, described reduction is with---processing of carrying out with finely divided sulphur if desired---is carried out in the presence of a kind of catalyst carrier, and described catalyst carrier is graphite or active carbon for example, preferred graphite.Platinum salt is before with finely divided sulphuring treatment, preferred especially and finely divided graphite mixes, usually with wherein greater than 90 weight %, be preferably greater than 95 weight % granularity 0.1-1000 μ m, preferably 1-300 μ m, especially preferably the graphite in the 2-100 mu m range mixes.

The mol ratio of platinum and carbon (or graphite or active carbon) is chosen in 0.001-10 weight %, preferred 0.01-5 weight %, particularly the 0.05-2 weight % scope usually.

According to former observation, the hydrogenation that the catalyst that obtains by the inventive method both had been suitable for organic compound also is suitable for the hydrogenation of inorganic compound.

Catalyst of the present invention is preferred for the hydrogenation of alefinically unsaturated compounds or acetylenically unsaturated compound, and described alefinically unsaturated compounds or acetylenically unsaturated compound be C for example 2-C 12Alkene and C 2-C 12Alkynes, preferred water miscible C 2-C 12Alkene and C 2-C 12Alkynes, special preferred aliphat C 2-C 12Alkene and aliphatic C 2-C 12Alkynes, preferred extremely especially propylene, butylene, amylene, propine, butine, pentyne; With the hydrogenation that is used for the extremely corresponding alcohol of carboxylic acid, aldehydes or ketones, described carboxylic acid is C for example 2-C 12Monocarboxylic acid and C 4-C 12Dicarboxylic acids, preferred water dissolubility C 2-C 12Monocarboxylic acid and water-soluble C 4-C 12Dicarboxylic acids, preferred especially acetate, propionic acid, butyric acid, glutaric acid, adipic acid, described aldehyde is C for example 2-C 12Aldehyde, preferred water dissolubility C 2-C 12Aldehyde, preferred especially acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, or nitrile is to the hydrogenation of corresponding amine.In addition, catalyst of the present invention is suitable for for example hydrogenation of oxygen of inorganic matter, but is particularly suitable for preparing hydroxyl ammonium salt by the hydrogenation of nitric oxide in aqueous inorganic acid.

The preparation of hydroxyl ammonium salt is carried out under hydrogen and nitric oxide production mol ratio are 1.5: 1 to 6: 1, preferred 1.6: 1 to 5: 1 situation usually.

The nitric oxide production hydrogenation temperature in 30-80 ℃, preferred 35-60 ℃ of scope is usually carried out.In addition, the pressure in the hydrogenation process is chosen in 1-30bar (absolute pressure), preferred 1.3-10bar (absolute pressure) scope usually.

Catalyst depends primarily on platinum and reactor pressure with the ratio of inorganic acid, is generally 5-100g, preferred every liter of inorganic acid of 10-30g platinum/graphite catalyst under the situation of platinum.

In another preferred embodiment, especially in the preparation of hydroxyl ammonium salt, before hydrogenation, catalyst is handled (" activation ") with hydrogen in acid solution, advantageously in the inorganic acid that carries out hydrogenation, handle.

According to observation so far, catalyst of the present invention is in the known catalysts that is better than being used for identical purpose aspect active, selectivity and service life---these two kinds of catalyst all not by the situation that for example sulphur is poisoned in set mode again under.Under premeditated situation of poisoning, the catalyst of regeneration is compared with the catalyst of not regenerating according to the present invention and take out from the catalyst of same basic total amount according to the present invention, for reaching identical activity, selectivity or service life, needs to add more sulphur.The advantage that the method for the present invention's preparation and regeneration hydrogenation catalyst also has is can reduce the amount of discarded catalyst, because described catalyst can use the longer time.The catalyst that time per unit must discharge and handle still less.

Embodiment 1: the mensuration of granularity

Use MALVERN Mastersizer to measure granularity (reaching each page thereafter for 24 (1990) the 36th pages referring to Verfahrenstechnik in addition).Measure the Fraunhofer diffraction (Fraunhofer diffraction) under the 633nm wavelength.By selecting the focal distance f=300mm of front lens, record the size distribution in the 1-600 mu m range.

For measuring, spoonful point powder to be detected is added to (BASF AG in Nekanils 910 aqueous solution of 1 liter of 0.1 weight % concentration; Nekanil 910 nonyl phenols that are a kind of and 9-10mol reacting ethylene oxide; Character: the liquid of transparent, colourless, thickness; Nonionic, 20 ℃ density: 1.04g/cm 3Pour point: below-10 ℃; The pH:6.5-8.5 of 1 weight % concentration solution).Before measuring, mixture to be detected was handled 1 minute with ultrasonic wave.

Embodiment 2: heat regeneration

The heat regeneration based on the hydrogenation catalyst of platinum of partly being poisoned by finely divided sulphur

Use 920kg to contain wet catalyst and carry out heat regeneration.Be dispersed in this catalyst on a plurality of containers and put into baking oven.Described 920kg catalyst is dispersed on 60 containers.

After in the baking oven of packing into, start heating schedule.

Described heating schedule is followed the temperature in the following table

Before handling and afterwards by the regeneration of analysis to measure monitoring heat.Importance is the improvement of the catalyst activity measured by the chemisorbed on the platinum in this.Before handling, record the chemisorbed value at 2000cm 2/ g-5000cm 2In/g the scope (a plurality of random samples of carbon monoxide-olefin polymeric), be generally 2500cm 2/ g.After the processing, the value that reaches is 5000cm 2/ g-8000cm 2/ g is generally 7000cm 2/ g.

In all samples, the mercury content before the heat regeneration on the graphite is 200-400mg/kg, after regeneration of the present invention, is 10-50mg/kg, is generally 20mg/kg.

The reaction rate of described catalyst was measured before heat regeneration.This speed is 0.01molN/h/g CatalystAfter the heat treatment, reaction rate increases to 0.09mol N/h/g Catalyst

Embodiment 3: chemical regeneration

The same catalyst (920kg contains wet catalyst in addition) that is used for heat regeneration is carried out chemical regeneration.

When carrying out chemical regeneration, can't increase the specific area of platinum, also can't reduce the content of mercury when not carrying out heat regeneration.Chemisorbed measured value before regeneration is 2000cm 2/ g-2800cm 2/ g.After the chemical regeneration, the chemisorbed value is at 2000cm 2/ g-2800cm 2Do not change between/the g.With afterwards, mercury content remains on 200-400mg/kg, is generally 350mg/kg, does not change before the chemical regeneration.

Embodiment 4: the chemical regeneration after the heat regeneration

After the heat regeneration in embodiment 3, make a 320kg carry out chemical regeneration with the catalyst that this mode is handled.For all random samples, platinum surface area described in the embodiment 3 and mercury concentration all remain in the scope that obtains among the embodiment 3.

Claims (6)

1. one kind makes the method based on the hydrogenation catalyst regeneration of platinum, wherein described hydrogenation catalyst based on platinum is carried out heat regeneration 50-600 ℃ temperature.
Claim 1 make method based on the regeneration of the hydrogenation catalyst of platinum, wherein said regeneration is carried out in a kind of protective atmosphere.
Claim 1 or 2 make method based on the regeneration of the hydrogenation catalyst of platinum, wherein with described hydrogenation catalyst based on platinum after heat treatment, then handle with strong acid.
4. according to each carried out the purposes based on the hydrogenation catalyst of platinum of regeneration among the claim 1-3, be used for hydrogenating organic compounds or inorganic compound.
The carrying out of claim 4 the purposes based on the hydrogenation catalyst of platinum of regeneration, be hydroxyl ammonium salt wherein with the hydrogenation of inorganic compound nitric oxide.
The carrying out of claim 4 the purposes based on the hydrogenation catalyst of platinum of regeneration, wherein organic compound alefinically unsaturated compounds or acetylenically unsaturated compound or carboxylic acid, aldehydes or ketones are carried out hydrogenation.
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